Palladium-Catalyzed Direct ortho-sulfonylation of. Azobenzenes with Arylsulfonyl Chlorides via C H. Table of Contents

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1 Electronic upplementary Material (EI) for RC Advances. This journal is The Royal ociety of Chemistry 205 upporting Information Palladium-Catalyzed Direct ortho-ulfonylation of Azobenzenes with Arylsulfonyl Chlorides via C H Activation Chengcai Xia, a, c Zhenjiang Wei, c Chao hen, b Jun Xu, b Yong Yang b, Weike u a* and Pengfei Zhang b,a* a Pharmacy College, Zhejiang University of Technologe, Hangzhou 3004, China b College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou China c Pharmacy College, Taishan Medical University, Tai an 2706, China Table of Contents.General Information Experimental ection Characterization data of the products H and 3 spectra of the products X-ray Crystal Data for catalyst 3b References...4 [a] Pharmacy College, Zhejiang University of Technology, Hangzhou 3004, China [b] College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou China chxyzpf@hotmail.com [c] Pharmacy College, Taishan Medical University, Tai an 2706, China

2 . General Information All the chemicals were obtained commercially and used without any prior purification. HNMR spectra were recorded on a Bruker AvanceII 500 spectrometer. All products were isolated by short chromatography on a silica gel ( mesh) column using petroleum ether (60-90 C) and ethyl acetate. unless otherwise noted. All compounds were characterized by, 3 and HRGC- HRM, which are consistent with those reported in the literature. 2. Experimental ection General procedure for preparation of azoxybenzenes R NH 2 CuBr (6 mol%) pyridine (8 mol%) air ( atm) toluene (2ml) All of the azo-compounds were prepared from arylamines, according to the literature. [] Mix CuBr (4.2 mg, 0.03 mmol), pyridine (8.7 mg, 0.09 mmol), arylamines (93 mg, mmol) in toluene (4 ml) under air ( atm). The reaction mixture was vigorously stirred at 60 C for 20 h. After cooling down to room temperature and concentrating in vacuum, the residue was purified by flash chromatography on a short R silica gel (eluent: petroleum ether) to afford azo-compound; yellow solid; General procedure for preparation ortho-sulfonylated azobenzenes R N N Cl H Pd(CH 3 CN) 2 Cl 2 (0 mol%) K 2 C 3 (2 equiv) 4A M (00 mg),4-dioxane (2 ml) a 2a 3a Mix azoic compound (0.5equiv), benzene sulfonyl chloride (0.6equiv), Pd(CH 3 CN) 2 Cl 2 (0 mol%), K 2 C 3 (2 equiv), 4A M (00 mg) in,4-dioxane (2 ml) under air. The reaction mixture was vigorously stirred at 30 C for 2 h. After 2

3 cooling down to room temperature and concentrating in vacuum, the residue was purified by flash chromatography on a short silica gel to afford the protect. 3. Characterization data of the products Diazene. (a) (E)-,2-di-p-tolyldiazene. btained as a yellow solid in90% yield; M.p o C.. (500 MHz, CDCl 3 ) δ 7.8 (d, J = 8.3 Hz, 4H), 7.30 (d, J = 8.0 Hz, 4H), 2.42 (s, 6H). 3 (26 MHz, CDCl 3 ) δ 50.85, 4.22, 29.73, 22.75, HRM (EI+): Calculated for C 4 H 4 N 2 : [M+H] , Found (E)-,2-di-m-tolyldiazene btained as a yellow solid in 87% yield; M.p o C. (500 MHz, CDCl 3 ) δ 7.7 (s, 4H), (m, 2H), 7.25 (d, J = 7.0 Hz, 2H), 2.42 (d, J = 3.0 Hz, 6H). 3 (26 MHz, CDCl 3 ) δ 52.87, 39.00, 3.75, 28.95, 22.97, 20.54, HRM (EI+): Calculated for C 4 H 4 N 2 : [M+H] , Found (E)-,2-bis(4-ethoxyphenyl)diazene. btained as a yellow solid in 92% yield; M.p.50-5 o C. (500 MHz, CDCl 3 ) δ (m, 4H), 6.98 (d, J = 8.9 Hz, 4H), 4.0 (q, J = 7.0 Hz, 4H),.44 (t, J = 7.0 Hz, 6H). 3 (26 MHz, CDCl 3 ) δ 6.0, 46.93, 24.36, 4.66, 63.79, 4.80.HRM (EI+): Calculated for C 6 H 8 N 2 2 : [M+H] , Found (E)-,2-bis(3-methoxyphenyl)diazene. btained as a yellow solid in 85% yield; M.p o C. (500 MHz, CDCl 3 ) δ 7.49 (ddd, J = 7.8,.6, 0.9 Hz, 2H), (m, 2H), 7.36 (t, J = 8.0 Hz, 2H), 6.98 (ddd, J = 8.2, 2.6, 0.8 Hz, 2H), 3.83 (s, 6H). 3 (26 MHz, CDCl 3 ) δ 59.3, 52.79, 28.76, 6.85, 6.4, 04.69, HRM (EI+): Calculated for 3

4 C 4 H 4 N 2 2 : [M+H] , Found (E)--(3-methoxyphenyl)-2-phenyldiazene. btained as a yellow solid in 60% yield; M.p o C. (500 MHz, CDCl 3 ) δ (m, 2H), (m, 6H), (m, H), 3.90 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 60.34, 53.9, 52.6, 3.05, 29.80, 29., 22.89, 7.83, 7.4, 05.74, HRM (EI+): Calculated for C 3 H 2 N 2 : [M+H] , Found (E)--(3-methoxyphenyl)-2-(m-tolyl)diazene. btained as a yellow liquid in 58% yield. (500 MHz, CDCl 3 ) δ 7.73 (d, J = 5.8 Hz, 2H), 7.55 (ddd, J = 7.8,.5,.0 Hz, H), (m, H), 7.4 (dd, J = 6.4, 8.3 Hz, 2H), 7.29 (d, J = 7.5 Hz, H), 7.03 (ddd, J = 8.2, 2.6, 0.8 Hz, H), 3.89 (s, 3H), 2.45 (s, 3H), 2.45 (s, H). 3 (26 MHz, CDCl 3 ) δ 60.32, 53.94, 52.68, 38.99, 3.83, 29.76, 28.9, 22.93, 20.55, 7.72, 7.04, 05.69, 55.47, HRM (EI+): Calculated for C 4 H 4 N 2 : [M+H] , Found (E)--phenyl-2-(2-tosylphenyl)diazene (3a) btained as a white solid in 78% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.40 (dd, J = 7.7,.5 Hz, H), (m, 4H), 7.65 (dtd, J = 22.0, 7.5,.4 Hz, 2H), 7.58 (dd, J = 7.7,.3 Hz, H), (m, 3H), 7.6 (d, J = 8.2 Hz, 2H), 2.32 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 52.72, 49.07, 43.9, 39.43, 38.88, 34.35, 3.97, 30.54, 29.35, 29.29, 29., 28.20, 23.77, 6.90, 2.5. HRM (EI+): Calculated for C23H8N23: [M+H] , Found (E)--(2-((4-bromophenyl)sulfonyl)phenyl)-2-phenyldiazene (3b) 4

5 Br btained as a orange solid in 66% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.39 (d, J = 7.8 Hz, H), (m, 4H), 7.7 (t, J = 7.6 Hz, H), 7.65 (t, J = 7.5 Hz, H), 7.60 (d, J = 7.8 Hz, H), (m, 3H), (m, 2H). 3 (26 MHz, CDCl 3 ) δ 52.68, 48.96, 4.34, 38.7, 34.82, 32.20, 3.96, 30.7, 29.78, 29.42, 29.23, 28.20, 23.67, HRM (EI+): Calculated for C 8 H 3 BrN 2 2 : [M+Na] , Found (E)--(2-((4-fluorophenyl)sulfonyl)phenyl)-2-phenyldiazene(3c) F btained as a orange solid in 86% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.40 (dd, J = 7.8,.4 Hz, H), (m, 2H), (m, 2H), 7.70 (dd, J = 7.7,.5 Hz, H), 7.65 (td, J = 7.6,.4 Hz, H), 7.60 (dd, J = 7.8,.3 Hz, H), (m, 3H), 7.03 (t, J = 8.6 Hz, 2H). 3 (26 MHz, CDCl 3 ) δ 52.69, 48.95, 38.43, 34.70, 32.6, 3.2, 3.05, 30.67, 29.35, 29.2, 23.66, 7.04, 6.0, HRM (EI+): Calculated for C8H3FN22: [M+Na] , Found (E)--(2-((4-nitrophenyl)sulfonyl)phenyl)-2-phenyldiazene (3d) N 2 btained as a pale yellow solid in 67% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.44 (d, J = 7.8 Hz, H), 8.9 (d, J = 8.2 Hz, 2H), 8.3 (d, J = 8.5 Hz, 2H), 7.74 (qd, J = 5., 7.5 Hz, 4H), 7.65 (d, J = 7.9 Hz, H), 7.55 (d, J = 5.8 Hz, 3H). 3 (26 MHz, CDCl 3 ) δ 52.57, 50.5, 48.90, 48.06, 37.29, 35.42, 32.50, 30.92, 29.65, 29.36, 23.90, 23.57, 7.2. HRM (EI+): Calculated for C 8 H 3 N 3 4 : [M+H] , Found (E)--(2-((4-methoxyphenyl)sulfonyl)phenyl)-2-phenyldiazene (3e) 5

6 btained as a white solid in 75% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.37 (d, J = 7.7 Hz, H), 7.87 (dd, J = 20.9, 6.6 Hz, 4H), 7.64 (dt, J = 2.9, 7.4 Hz, 2H), 7.55 (dd, J = 2.8, 6.5 Hz, 4H), 6.82 (d, J = 8.4 Hz, 2H), 3.76 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 63.2, 52.75, 49.02, 39.6, 34.23, 33.8, 3.95, 30.54, 29.6, 23.75, 6.92, 3.87, HRM (EI+): Calculated for C 9 H 6 N 2 3 : [M+H] , Found (E)--(2-((3-nitrophenyl)sulfonyl)phenyl)-2-phenyldiazene (3f) N 2 btained as a yellow solid in 63% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.92 (s, H), 8.46 (d, J = 7.8 Hz, H), 8.32 (d, J = 8. Hz, H), 8.23 (d, J = 7.8 Hz, H), 7.79 (dd, J = 3., 2. Hz, 2H), (m, 2H), 7.64 (d, J = 7.8 Hz, H), 7.56 (ddd, J = 9.7, 5.2, 4.3 Hz, 4H). 3 (26 MHz, CDCl 3 ) δ 52.48, 48.85, 47.95, 44.55, 37.37, 35.39, 33.7, 32.55, 30.89, 30.09, 29.6, 29.39, 27.50, 23.75, 23.59, HRM (EI+): Calculated for C 8 H 3 N 3 4 : [M+H] , Found (E)--(2-(naphthalen-2-ylsulfonyl)phenyl)-2-phenyldiazene (3g) btained as a pale yellow solid in 84% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.64 (s, H), 8.64 (s, H), (m, H), (m, H), 7.86 (dd, J = 22.7, 8.8 Hz, 3H), 7.78 (d, J = 8. Hz, 3H), 7.70 (ddd, J = 9.2, 6.0,.8 Hz, 2H), (m, 2H), (m, 4H). 3 (26 MHz, CDCl 3 ) δ 52.72, 49.00, 38.98, 38.59, 34.97, 34.59, 32.0, 3.95, 30.63, 30.9, 29.46, 29.7, 29., 28.96, 27.87, 27.36, 23.76, 23.03, HRM (EI+): Calculated for C 22 H 6 N 2 2 : [M+H] , Found

7 (E)-3,5-dimethyl-4-((2-(phenyldiazenyl)phenyl)sulfonyl)isoxazole. (3h) N btained as a white solid in 90% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.37 (d, J = 7.9 Hz, H), 7.77 (t, J = 7.6 Hz, H), (m, 3H), 7.56 (dd, J = 2.3, 7.0 Hz, 4H), 2.50 (s, 3H), 2.9 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 74.00, 57.64, 52.98, 49.64, 37.80, 35.0, 32.9, 30.43, 29.24, 29.3, 23.30, 7.89, 7.64, 3.04, 0.8. HRM (EI+): Calculated for C7H5N33: [M+H] , Found (E)--phenyl-2-(2-(thiophen-2-ylsulfonyl)phenyl)diazene. (3i) btained as a white solid in 87% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.37 (d, J = 8.0 Hz, H), (m, 2H), (m, H), (m, 2H), (m, H), (m, 4H), 7.00 (t, J = 4.4 Hz, H). 3 (26 MHz, CDCl 3 ) δ 52.67, 49.00, 43.44, 39.35, 34.53, 34.38, 34.06, 32.2, 30.82, 29.25, 29.2, 27.23, 24.09, HRM (EI+): Calculated for C 6 H 2 N : [M+H] , Found (E)--(2-((5-chloro-3-methylbenzo[b]thiophen-2-yl)sulfonyl)phenyl)-2- phenyldiazene. (3j) Cl btained as a pale yellow solid in 89% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.45 (d, J = 7.7 Hz, H), 7.87 (d, J = 7.5 Hz, H), 7.76 (t, J = 7.6 Hz, H), (m, H), 7.52 (q, J = 5.3 Hz, H), 7.38 (d, J = 8.7 Hz, H), 2.5 (d, J = 0.6 Hz, H). 3 (26 MHz, CDCl 3 ) δ 52.46, 49.4, 40.55, 39.83, 38.46, 37.09, 34.9, 32.5, 3.3, 30.53, 29.58, 28.98, 27.89, 24.2, 23.63, 23.2, 7.7, HRM (EI+): Calculated for C 2 H 5 N : [M+H] , Found

8 (E)-methyl 3-((2-(phenyldiazenyl)phenyl)sulfonyl)thiophene-2-carboxylate. (3k) btained as a pale yellow solid in 73% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.54 (dd, J = 5.6, 3.6 Hz, H), 7.85 (d, J = 5.2 Hz, H), (m, H), (m, H), 7.49 (d, J = 7.6 Hz, H), 7.39 (d, J = 5.3 Hz, H), 3.7 (s, H). 3 (26 MHz, CDCl 3 ) δ 59.44, 54.45, 52.40, 5.33, 46.00, 45.89, 39.06, 34.8, 32.02, 3.79, 30., 30.09, 28.90, 23.69, 6.34, HRM (EI+): Calculated for C 8 H 4 N : [M+H] , Found (E)--phenyl-2-(2-(phenylsulfonyl)phenyl)diazene. (3l) btained as a orange solid in90% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.43 (dd, J = 7.8,.5 Hz, H), 7.95 (dt, J = 6.3, 2.0 Hz, 2H), (m, 2H), 7.68 (dtd, J = 22.5, 7.5,.5 Hz, 2H), (m, H), (m, 3H), (m, H), 7.37 (dd, J = 0.6, 4.9 Hz, 2H). 3 (26 MHz, CDCl 3 ) δ 46.56, 43.29, 42.32, 38.53, 34.56, 32.96, 32.04, 30.59, 29.46, 29., 28.66, 28.05, 23.77, HRM (EI+): Calculated for C 8 H 4 N : [M+H] , Found (E)--(2-((4-chlorophenyl)sulfonyl)phenyl)-2-phenyldiazene. (3m) Cl btained as a orange solid in 82% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.40 (dd, J = 7.8,.4 Hz, H), (m, 2H), (m, 2H), 7.7 (td, J = 7.6,.5 Hz, H), 7.65 (td, J = 7.6,.4 Hz, H), (m, H), (m, 3H), (m, 2H). 3 (26 MHz, CDCl 3 ) δ 52.65, 48.94, 40.76, 39.6, 38.9, 34.79, 32.7, 30.68, 29.69, 29.40, 29.20, 28.95, 23.65, HRM (EI+): Calculated for C 8 H 4 N : [M+H] , Found

9 (E)--(2-((4-(tert-butyl)phenyl)sulfonyl)phenyl)-2-phenyldiazene. (3n) btained as a orange solid in 9% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.4 (dd, J = 7.7,.5 Hz, H), (m, 2H), (m, 2H), (m, 2H), (m, H), (m, 3H), (m, 2H),.22 (d, J = 3.3 Hz, 9H). 3 (26 MHz, CDCl 3 ) δ 56.8, 52.66, 49.3, 39.3, 38.77, 34.40, 3.98, 30.54, 29.28, 29.07, 27.89, 25.7, 23.78, 6.92, 35.08, HRM (EI+): Calculated for C 8 H 4 N : [M+H] , Found (E)--(4-methyl-2-tosylphenyl)-2-(p-tolyl)diazene(3o) btained as a orange solid in 86% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.23 (s, H), 7.87 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 8.2 Hz, 2H), 7.55 (d, J = 8. Hz, H), 7.47 (dd, J = 8.,. Hz, H), 7.33 (d, J = 8. Hz, 2H), 7.9 (d, J = 8. Hz, 2H), 2.54 (s, 3H), 2.48 (s, 3H), 2.34 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 50.9, 47.03, 43.72, 42.46, 4.26, 39.60, 38.53, 34.88, 29.73, 29.62, 29.23, 28.4, 23.73, 6.73, 2.6, 2.53, HRM (EI+): Calculated for C2H20N22: [M+H] , Found (E)--(5-methyl-2-tosylphenyl)-2-(m-tolyl)diazene. (3p) btained as a white solid in 75% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.30 (d, J = 8. Hz, H), 7.86 (d, J = 8.3 Hz, 2H), 7.67 (d, J = 7.9 Hz, H), 7.60 (s, H), (m, 2H), (m, 2H), 7.20 (d, J = 8. Hz, 2H), 2.48 (d, J = 0. Hz, 6H), 2.35 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 9

10 52.80, 49.06, 45.57, 43.66, 39.72, 38.95, 35.9, 32.69, 30.96, 29.45, 29.24, 28.92, 28.04, 23.82, 2.45, 7.8, 2.62, 2.54, HRM (EI+): Calculated for C2H20N22: [M+H] , Found (E)--(4-ethoxy-2-tosylphenyl)-2-(4-ethoxyphenyl)diazene. (3q) btained as a white solid in 83% yield; M.p o C. (500 MHz, CDCl 3 ) δ 7.9 (d, J = 2.7 Hz, H), 7.86 (d, J = 8.3 Hz, 2H), 7.79 (d, J = 8.9 Hz, 2H), 7.69 (d, J = 8.9 Hz, H), 7.9 (d, J = 8. Hz, 2H), (m, H), (m, 2H), 4.23 (q, J = 7.0 Hz, 2H), 4.6 (d, J = 7.0 Hz, 2H), 2.34 (s, 3H),.52 (d, J = 6.9 Hz, 3H),.49 (d, J = 6.9 Hz, 3H). 3 (26 MHz, CDCl 3 ) δ 6.77, 60.33, 47.3, 43.7, 42.76, 40., 39.6, 29.22, 28.07, 25.53, 20.75, 8.35, 4.60, 3.75, 64.55, 63.90, 2.53, 4.77, HRM (EI+): Calculated for C 23 H 24 N 2 4 : [M+H] , Found (E)--(5-methoxy-2-tosylphenyl)-2-(3-methoxyphenyl)diazene. (3r) btained as a orange solid in 85% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.33 (d, J = 8.7 Hz, H), 7.85 (d, J = 8.3 Hz, 2H), (m, H), 7.45 (t, J = 8.0 Hz, H), (m, H), 7.8 (d, J = 8. Hz, 2H), (m, 3H), 3.93 (s, 3H), 3.90 (s, 3H), 2.33 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 64.5, 60.33, 53.79, 50.7, 43.56, 40.06, 3.45, 30.97, 29.82, 29.3, 27.80, 8.86, 8.0, 6.9, 06.73, 0.29, 55.98, 55.56, 2.5. HRM (EI+): Calculated for C2H20N24: [M+H] , Found (E)--(3-methoxyphenyl)-2-(2-tosylphenyl)diazene. (3s) 0

11 btained as a orange solid in 5% yield; M.p o C. (500 MHz, CDCl 3 ) δ 8.39 (dd, J = 7.7,.5 Hz, H), 7.85 (d, J = 8.3 Hz, 2H), (m, 2H), 7.58 (dd, J = 7.7,.4 Hz, H), (m, 2H), 7.37 (dd, J = 5.0, 3. Hz, H), 7.7 (d, J = 8.0 Hz, 2H), (m, H). 3 (26 MHz, CDCl 3 ) δ 60.42, 49.0, 43.93, 39.37, 38.70, 37.02, 34.38, 30.58, 29.80, 29.46, 29.35, 28.2, 8.76, 7.98, 6.93, 06.76, 55.56, HRM (EI+): Calculated for C 20 H 8 N 2 3 : [M+H]+ 367., Found (E)--(5-methoxy-2-tosylphenyl)-2-phenyldiazene.(3t) btained as a orange solid in 7% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.32 (d, J = 8.7 Hz, H), (m, 4H), (m, 3H), 7.5 (d, J = 8. Hz, 2H), (m, 2H), 3.89 (s, 3H), 2.3 (s, 3H). 3 C NMR (26 MHz, CDCl 3 ) δ 64.3, 52.57, 50.7, 43.54, 40.00, 32.05, 3.36, 3., 29.23, 29.2, 27.94, 23.84, 6.5, 0.22, 55.97, 2.5. HRM (EI+): Calculated for C20H8N23: [M+H]+ 367., Found (E)--(5-methoxy-2-tosylphenyl)-2-(m-tolyl)diazene.(3u) btained as a orange solid in 8% yield; M.p o C. H NMR (500 MHz, CDCl 3 ) δ 8.32 (d, J = 8.8 Hz, H), 7.83 (d, J = 8.3 Hz, 2H), 7.65 (d, J = 7.8 Hz, H), 7.58 (s, H), 7.4 (t, J = 7.7 Hz, H), 7.34 (d, J = 7.5 Hz, H), 7.7 (d, J = 8.3 Hz, 2H), 7.0 (dd, J = 8.8, 2.6 Hz, H), 7.07 (d, J = 2.6 Hz, H), 3.89 (s, 3H), 2.47 (s, 3H), 2.33 (s, 3H). 3 (26 MHz, CDCl 3 ) δ 64.4, 52.67, 50.79, 43.48, 40.06, 38.98, 32.84, 3.35, 30.95, 29.22, 28.92, 27.89, 23.93, 2.57, 6.04, 0.9, 55.95, 2.53, HRM (EI+): Calculated for C2H20N23: [M+H] , Found

12 4. H and 3 spectra of the products 3 2

13 3 3

14 3 4

15 3 5 N

16 6

17 3 3 7

18 3a 3 8

19 3a 3b 3 9

20 3b 3c F 3 20

21 3c F 3d 3 2

22 3d 3e 3 22

23 3e 3f N

24 3f N 2 3g 24

25 3 3g N 3h 25

26 3 3h N 3i 3 26

27 3i N N 3j Cl 3 27

28 N N 3j Cl 3k 3 28

29 3k 3l 29

30 3 C NM 3l 3m Cl 30

31 3 3m Cl 3n 3 3

32 3n 3o 3 32

33 3o 3p 3 33

34 3p 3q 3 34

35 3q 3r 3 35

36 3r 3s 3 36

37 3s 3t 3 37

38 3t 3u 3 38

39 3u 5. X-ray Crystal Data for GPT-Pd catalyst 3b Crystals of GPT-Pd catalyst 3c (C 8 H 3 BrN 2 2 ) were recrystallized from a trichloromethane solution. A single white needle crystal which was suitable for X-ray diffraction measurements was mounted on a glass fiber. Unit cell measurements and intensity data collections were performed on a Rigaku AFC7R diffractometer with graphite monochromated Mo Ka. The data reduction included a correction for Lorentz and polarization effects, with an applied multi-scan absorption correction (ADAB). The crystal structure was solved and refined using the HELXTL-97 program suite. Direct methods yielded all non-hydrogen atoms which were refined with anisotropic thermal parameters. The reflection data were consistent with a monoclinic system: P2()/c. The obtained crystal structure has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number: (CCDC N). The crystallographic data and refinement parameters of 3c are listed in Table. 39

40 Table. Crystallographic data and structure refinement for 3b. Identification code Empirical formula C 8 H 3 BrN 2 2 Formula weight Temperature, K 296(2) K Wavelength, Å Å Crystal system monoclinic pace group P2/c Cell dimensions a, b, c, Å 7.89(2) Å, 8.770(5) Å,.594(3) Å α, β, γ, o o, (5) o, o Volume, Å (8) Å 3 Z 4 Calculated density, g/cm Absorption coefficient, mm F (000)

41 Crystal size, mm Theta range for data collection, o Limiting indices 0.22 x 0.2 x 0.20 mm 2.08 to 25.0deg -9<=h<=7, -2<=k<=22, -3<=l<=3 Completeness to theta = 25.0 o 99.8 % Absorption correction multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 3037 / 0 /27 Goodness of fit on F 2.07 R indices [I > 2σ(I)] R = , wr2 = R indices (all data) R = , wr2 = Largest diff. peak and hole, e Å and e.a^-3 6.References [] C. Zhang, N. Jiao, Angew. Chem, Int. Ed. 200, 49,